EP3082547A1 - Tissus de nettoyage grand public à usages multiples et leurs procédés de fabrication - Google Patents

Tissus de nettoyage grand public à usages multiples et leurs procédés de fabrication

Info

Publication number
EP3082547A1
EP3082547A1 EP16706786.7A EP16706786A EP3082547A1 EP 3082547 A1 EP3082547 A1 EP 3082547A1 EP 16706786 A EP16706786 A EP 16706786A EP 3082547 A1 EP3082547 A1 EP 3082547A1
Authority
EP
European Patent Office
Prior art keywords
substrate
texture layer
scrubbing
cloth
scrubbing cloth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16706786.7A
Other languages
German (de)
English (en)
Other versions
EP3082547B1 (fr
Inventor
Paul N. Daveloose
Matthew S. COLE
Ibrahim S. GUNES
Irem Bolukbasi
Ann M. GILMAN
Matthew R. Smith
David C. Raithel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP3082547A1 publication Critical patent/EP3082547A1/fr
Application granted granted Critical
Publication of EP3082547B1 publication Critical patent/EP3082547B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/16—Cloths; Pads; Sponges
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/16—Cloths; Pads; Sponges
    • A47L13/17—Cloths; Pads; Sponges containing cleaning agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D27/00—Woven pile fabrics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene

Definitions

  • the present disclosure relates to scrubbing articles having a textured surface or surfaces. More particularly, the present disclosure relates to a scrubbing cloth having opposed first and second surfaces formed to have different properties relative to one another and a texture layer formed on at least one of the first and second surfaces to provide a multipurpose scrubbing cloth having enhanced surface treating capabilities.
  • the differently formed surfaces can provide one relatively more absorbent side of the scrubbing cloth and/or one relatively higher, fluffier, loftier, less dense side of the scrubbing cloth, either temporarily or permanently.
  • a variety of cleaning articles in the form of pads, wipes and cloths have been developed and made commercially available for household and industrial use. Consumers oftentimes desire to use the articles for cleaning or surface treating tasks requiring scrubbing which in turn may include various degrees of wiping, abrading and/or scouring. For example, it can be difficult, if not impossible, to remove dried food from a countertop using an inherently soft article. Conversely, however, consumers strongly prefer that the article not be overly rigid. In some cases, consumers thus desire that the article be drapable for ease of use. Furthermore, consumers often desire a scrubbing cloth that is reusable and that is not overly abrasive on relatively soft or easily scratched surfaces.
  • the scrubbing wipe article of Johnson et al. can be used "dry” or can be loaded with a chemical solution.
  • U.S. Patent App. Pub. No 2006/0286884 to Thioliere et al. describes a wiping article comprising a liquid-absorbent web material and abrasive areas comprising cured particulate binder material disposed on a surface of the web.
  • the web material may include woven, knitted and non-woven materials.
  • Non-woven materials may include dry-laid, wet-laid and spun-bonded materials.
  • Suitable binder materials are disclosed that can be cured by heating, cooling or ultraviolet light.
  • U.S. Patent App. Pub. No. 2007/0212965 to Smith et al. describes a flexible scrubbing material that combines at least two discrete components, one being a continuous flexible substrate and one a discontinuous abrasive layer affixed to the flexible substrate.
  • the abrasive layer is a set of plates formed from a material different than the continuous flexible substrate.
  • the plate material is a printable material that subsequently solidifies, such as epoxy.
  • Smith et al. teach that the abrasive plates can be formed from a solidified material such as ultraviolet or thermally curable polymeric materials with or without abrasive particles embedded inside. Smith et al.
  • a technique for printing the plates onto the substrates such as conventional screen-printing, UV etching and roller- printing.
  • An adhesive is sprayed on the fabric prior to application of the plates.
  • Smith et al. teaches an embodiment having two surfaces with different abrasion levels where the abrasion levels are provided on two separate substrates that may be assembled together or laminated to another substrate to form a scrub pad. Alternately, a single printed fabric can be stitched to an intermediate layer to form a composite (multiple-layer substrate) scrubbing cloth.
  • cleaning wipe constructions include or incorporate mildly abrasive particles within or at a surface of the base substrate.
  • U.S. Patent No. 5,213,588 to Wong et al. describes an abrasive wipe consisting of a paper towel-like base substrate having printed thereon a mixture containing irregularly-shaped polymeric particles.
  • U.S. Patent No. 4, 142,334 to Kirsch et al. describes a scouring and cleaning cloth having a coating of a solid binding agent on at least a portion of each surface in an open pattern applied by a printing process.
  • Kirsch et al. teach a consolidated nonwoven fabric having a pattern printed on its surface such that the pattern can be pressed down into the nonwoven fabric so as to produce an even surface.
  • Kirsch et al. do not describe opposed, differently formed surfaces of the fabric prior to printing the described patterns, nor a fabric having only one consolidated side or surface.
  • scrubbing articles having textured surfaces may be used to form scrubbing articles having textured surfaces.
  • a cleaning or scrubbing cloth formed of a single layer substrate having one surface treated to form a relatively more absorbent side and a texture layer formed on at least one surface is not presently available.
  • a scrubbing cloth formed of a single layer substrate having a fluffy, lofty, less dense or relatively higher surface i.e., fibers of the substrate project a distance from a mid-plane of the substrate
  • an opposed relatively flat, less lofty, more dense, lower surface with a texture layer provided on at least one of the surfaces is not presently available.
  • Such multipurpose cloths would advantageously allow for both non-abrasive wiping and/or liquid absorption as well as scouring/abrading actions to be accomplished with a single scrubbing article simply by reversing the side of the cloth being applied to the surface to be treated.
  • Scrubbing cloths of the present disclosure may take a variety of forms that include opposed, differing surfaces (e.g., differing relative loft, height, fluff, absorptive properties etc.) and a texture layer formed on at least one of the surfaces.
  • the scrubbing cloth includes a substrate having a first surface and a second surface opposite the first surface where the first surface has a first degree of loftiness and the second surface has a second degree of loftiness and the first degree of loftiness is greater than the second degree of loftiness.
  • the scrubbing cloth includes a substrate having a substrate having first and second surface opposed surfaces where at least one of the first and second surfaces is more absorptive than the other. At least one of the first and second surfaces of the various disclosed substrates include a texture layer formed thereon. Formation of the texture layer can be accomplished via various techniques and the texture layer composition may be formed of various materials.
  • the first surface of the cloth can have a first height greater than a second height of the second surface and the second surface can have a density greater than a density of the first surface.
  • the scrubbing cloth has a first, lofty or fluffy surface and an opposed, second, less lofty or flat surface while according to alternative embodiments, the relative loft, density and height of opposed surfaces of a scrubbing cloth are equal and the substrate forming the scrubbing cloth is treated on one side to form a side or surface having different absorptive properties relative to the opposed side or surface.
  • Scrubbing cloths described may form multipurpose and/or reusable scrubbing cloths.
  • Scrubbing cloths according to the disclosure comprise a single-layer substrate made of various fabrics including any of a woven, knitted, and non-woven material or combinations thereof.
  • a texture layer may be formed on the relatively flatter surface while the flatter surface remains permanently flattened.
  • the flatter surface may be formed to only temporarily be flatter such that the texture layer may be formed thereon more readily while the surface is in a flattened configuration.
  • a texture layer may be formed on the relatively loftier (fluffier) surface while the flatter surface remains permanently in a relatively flat, less lofty configuration.
  • a texture layer may be formed on both a loftier surface as well as on an opposed relative flat surface and still result in a cleaning article that provides multipurpose cleaning actions (given the relative differences in the surface portions that are not textured).
  • a texture layer may be formed on a surface of a substrate having one side that is more absorbent than an opposed side.
  • Methods according to the present disclosure include formation of a scrubbing cloth having a textured layer formed thereon including treating one side of a substrate to form a treated surface having surface characteristics differing from that of an opposed side of the substrate.
  • the opposed side of the substrate may be untreated or may be left undisturbed by the treatment of the treated side.
  • the opposed side may form a first, lofty surface and the treated side may form a second, flattened or less lofty surface.
  • the treated side forms a more absorptive surface and the opposed side forms a less absorptive surface.
  • Treatment can be achieved via various processing methods including calendaring, heat compression, flame treating, melting, cutting, removing fiber height, plasma treatment, spraying, flame treatment or electrical discharge.
  • a texture layer is formed on at least one surface of the substrate to form a scrubbing cloth.
  • FIG. 1 is a perspective view of a scrubbing cloth in accordance with an embodiment of the present disclosure
  • FIG. 2 is an enlarged plan view of the textured surface of the scrubbing cloth of FIG. i ;
  • FIG. 3 is an enlarged, cross-sectional view of a portion of the cloth of FIG. 1 taken along the lines 3-3, shown in FIG. 1;
  • FIG. 4 is an enlarged, cross-sectional view of a scrubbing cloth in accordance with an embodiment of the present disclosure
  • FIG. 5A is a plan view of a first surface of a scrubbing cloth illustrating fibers on a first side of a substrate;
  • FIG. 5B is a plan view of an opposed surface of the scrubbing cloth of FIG. 5 A, illustrating fibers on a second side of the substrate in accordance with an embodiment of the present disclosure
  • FIG. 6A is a photograph of a portion of an exemplary substrate folded at a corner to show first and second surfaces of the substrate, in accordance with an embodiment of the present disclosure
  • FIG. 6B is a photograph of one side of a scrubbing cloth formed from the substrate of FIG. 6A, in accordance with an embodiment of the present disclosure
  • FIG. 7A is a photograph of a portion of a textured surface of an exemplary scrubbing cloth, in accordance with the present disclosure.
  • FIG. 7B is a photograph of a portion of the scrubbing cloth of FIG. 7A folded at a corner of the cloth to show both the textured surface and an opposed surface of the scrubbing cloth of FIG. 7 A;
  • FIG. 8 is a view of the cloth portion of FIG. 3 being applied to a surface
  • FIGS. 9A-9B are top views of alternative embodiments of a scrubbing cloth in accordance with the present disclosure
  • FIG. 10 is a simplified illustration of a substrate during a method of manufacture in accordance with an embodiment of the present disclosure.
  • FIG. 11 is a simplified illustration of a method of manufacture of a scrubbing cloth in accordance with an embodiment of the present disclosure.
  • FIG. 12 is a cross-sectional, enlarged side view of a scrubbing cloth in accordance with an embodiment of the present disclosure.
  • FIG. 13 is a side cross-sectional view of a portion of a scrubbing cloth in accordance with an embodiment of the present disclosure.
  • FIG. 1 illustrates an embodiment of a scrubbing cloth 10 in accordance with the present disclosure.
  • Scrubbing cloth 10 may be described as a consumer cleaning or scrubbing cloth 10.
  • the term “consumer” is in reference to any household, cosmetic, industrial, hospital or food industry applications and the like of the cloth 10. Certain embodiments can be used as floor pads or hand pads, for example.
  • the term “scrubbing” is used to describe surface treating and may include cleaning, abrading and/or scouring, including various levels or degrees of abrading and/or scouring action (e.g., heavy duty, non-scratch, etc.).
  • the cloth 10 comprises a substrate 12 and a texture layer 14 (referenced generally in FIG. 1).
  • the substrate 12 and the texture layer 14 can comprise a variety of different materials as described further below.
  • the scrubbing cloth is characterized as including opposed sides having differing surfaces or sides (e.g., 16, 18) and a texture layer 14 formed on and perhaps at least partially penetrates at least one surface of the substrate 12 to provide a multipurpose cleaning article.
  • the substrate 12 defines first and second opposing surfaces (also described as sides) 16, 18 which form first and second opposed surfaces of the scrubbing cloth 10.
  • the scrubbing cloth 10 is formed from a single (non-laminated) substrate/fabric 12 (as used herein, the terms substrate and fabric are interchangeable)
  • the surfaces 16, 18 of the fabric 12 likewise form the surfaces 16, 18 of the scrubbing cloth 10.
  • a texture layer 14 is formed on one or both of the surfaces 16, 18 of the substrate 12 to form the scrubbing cloth 10.
  • a texture layer 14 is formed on surface 18 in the embodiment of FIG. 1.
  • the scrubbing cloth 10 further includes a chemical (e.g., a solid or a solution, not shown) loaded into, or absorbed by, the substrate 12.
  • a chemical e.g., a solid or a solution, not shown
  • the chemical may be formed on the cloth surface (e.g., via drying, spraying etc.) or may be provided as part of the texture layer composition 14. Applicable chemicals are likewise described in greater detail below.
  • the texture layer 14 may be configured to accommodate a wide variety of chemicals including those that are neutral, cationic, or anionic. Further, the scrubbing cloth 10 is equally useful without a chemical formulation.
  • the scrubbing cloth 10 may be described as a multipurpose scrubbing cloth formed to have a lofty, fluffy surface on one side (e.g., 16) and a relatively less lofty, flat or smooth surface on an opposed side/surface (e.g., 18).
  • the loftier side or surface 16 of scrubbing cloth 10 has an average fiber height that is higher than an average fiber height of the less lofty or flat side/surface 18 of the scrubbing cloth 10 (where height is in reference to a mid-plane M, FIG. 5, discussed below).
  • one side (e.g., 16) of substrate 12 may be treated to provide a relatively more or less absorbent side.
  • substrate 12 may be manufactured in a variety of ways.
  • One side (e.g., 18) of the substrate 10 may be configured to be treated (e.g., consolidated) only temporarily so that a texture layer 14 can more readily or easily be formed thereon. In this case, after the texture layer 14 is deposited or formed on the treated surface 18, the fibers of the treated surface portions not having texture composition thereon (e.g., 28, FIGS.
  • surface 18 may be configured to be treated (e.g., flattened, less lofty, or have less height relative to an opposed surface 16) permanently in which case the fibers of surface 18 would remain in the flattened, less lofty, less high state throughout the life (usage) of the cloth 10.
  • the substrate 12, when initially formed into a fabric may be manufactured in such a way so as to provide the relative fluffy and flat opposed surfaces 16, 18 at the time of formation of the fabric itself.
  • the flat surface e.g., 18
  • the flat surface would likewise remain in a relatively flattened or smooth (less lofty) state throughout the life (usage) of the cloth.
  • the term "flat" when used to describe a surface of cloth 10 (or of substrate 12) is intended to define surface characteristics including: generally uniform, uniform, completely flat, substantially flat, smooth, consolidated, more dense, less lofty (i.e., having a lesser degree of loftiness), less fluffy, shorter, lower height and/or having fibers of the surface that lie generally in the same plane, where the terms "more” and “less” are relative to an opposed side/surface.
  • the term "fluff or "fluffy” as used herein to describe an opposed surface of cloth 10 (or substrate 12) is intended to define surface characteristics including: open, lofty (i.e., having a greater degree of loftiness, less dense, non-consolidated, non- compacted, higher, or greater height, where the terms “more” and “less” are relative to an opposed side/surface .
  • lofty i.e., having a greater degree of loftiness, less dense, non-consolidated, non- compacted, higher, or greater height, where the terms “more” and “less” are relative to an opposed side/surface .
  • absorbent absorbent
  • absorptive absorbent
  • absorbing as used to describe scrubbing cloths according to embodiments of the present disclosure are defined as having the ability to absorb a material (e.g., a liquid) reversibly, at least to some degree. Stated otherwise, an absorbent material can be defined as one that a liquid can penetrate into and, rather than trap and irreversibly hold the liquid, the material may release the liquid either by evaporation (drying) or physical force (e.g., hand pressure/wringing).
  • a more absorbent side or surface of a substrate may more readily or to a greater degree absorb a liquid than an opposed side of the substrate and the liquid absorbed is able to at least partially be removed from the substrate, for example, by hand (e.g., wringing) or by drying.
  • the scrubbing cloth 10 may be described as providing a "scrubbiness" or abrasive attribute that is given by the texture layer 14 formed on at least one side or surface of the substrate 12. Conversely, the scrubbing cloth 10 provides a wiping or non-abrasive attribute on a side opposing the abrasive surface/side.
  • the term "scrubbiness" is in reference to an ability to abrade or remove a relatively small, undesirable item otherwise affixed to a surface as the cloth is moved back and forth over the item, as described more fully below.
  • a substrate can be given a scrubbiness characteristic not only by forming a hardened scrubbing material (i.e., texture layer) on the substrate's surface that may be at least as hard as or harder than the substrate itself, but also via the extent to which the so-formed material extends from or beyond the substrate surfaces or fibers, in conjunction with side-to-side spacing between individual sections of the scrubbing material.
  • a hardened scrubbing material i.e., texture layer
  • the scrubbing cloth 10 is characterized as having a lofty, fluffy surface (e.g., 16) on one side and a relatively less lofty, flat or smooth surface (e.g., 18) on an opposed side where the loftier side or surface 16 of scrubbing cloth 10 includes fibers 50 having an average fiber height that is higher than an average fiber height of the less lofty surface 18.
  • the terms "loft” or “loftiness” as used in this specification are in reference to the spacing or "openness" of fibers 50 otherwise forming the surface/area/volume in question.
  • a first surface/area/volume with fewer fibers per unit area or volume as compared to a second surface/area/volume comprised of the same denier fibers is considered to have a higher degree of loftiness.
  • loft or loftiness can be defined in terms of bulk density. "Bulk density" is the weight of a given fabric per unit volume. The fabric thickness can be measured in many ways; one accurate method employs an optical scanning technique.
  • FIG. 3 shows a cross-sectional view of a portion of the cloth 10 of FIG. 1 (where the orientation of FIG. 3 is such that the cloth 10 is facing the opposite direction relative to the orientation of FIG. 1, i.e., the textured surface 18 is facing up in the orientation of FIG. 1 and down in Fig. 3).
  • the opposed surfaces 16, 18 of the scrubbing cloth 10 include fibers 50a, 50b, respectively. It is to be understood that the fibers 50a, 50b are formed of the same substrate material or base fiber 50 and the different references are intended to show the differences in the characteristics of the fiber 50 at the various surfaces 16, 18.
  • the term "height" as used in this specification is in reference to extension of the fibers 50a, 50b and thereby the surfaces 16, 18 beyond (or “above” for fibers 50a relative to the orientations of FIGS. 3 and 8) relative to a mid-plane M that is otherwise generally parallel to a planar orientation of the substrate 12 (e.g., parallel to the first and second surfaces 16, 18 when the first and second surfaces 16, 18 are otherwise lying in a generally flat plane such as when the cloth 10 is placed on a secondary, generally flat surface or object (e.g., table T, FIG. 7B)), it being understood that even when placed on an otherwise flat secondary object, the first surface 16 is not "flat” as that term is used herein to describe the second surface 18).
  • the height of the first surface 16 can be measured from/relative to the second surface 18, such as depicted in FIG. 4. Measurement of fibers 50a relative to the second surface 18 (rather than relative to a mid-plane M) may be particularly useful in the case where a fabric is initially formed to have a flat second surface 18, since fibers 50 are knitted or woven to project in a direction outwardly opposite to the second surface 18 (i.e., upwardly with respect to the orientation of FIG. 4), described in further detail below.
  • FIG. 5A is a plan view of first surface 16 of scrubbing cloth 10 illustrating fibers 50a (referenced generally) on a first side of a scrubbing cloth 10 as well as a portion of a texture layer 14 formed on the first surface 16.
  • FIG. 5B is a plan view of an opposed surface of the scrubbing cloth of FIG. 5 A, illustrating fibers 50b (referenced generally) on a second side of the cloth 10.
  • the substrate 12 has a uniform material construction (i.e., the substrate 12 is comprised of a single, uniform material/composition and is a single, non-laminated layer), and is processed to generate the differing first and second surfaces 16, 18.
  • the substrate 12 is formed (at least temporarily) such that the first surface 16 has a first degree of loftiness and a first height hi while the second surface 18 has a second degree of loftiness and a second height h 2 (FIG. 3).
  • the scrubbing cloth 10 is formed of only a single layer substrate 12, the loftiness and height of each of the first and second surfaces of the substrate form the loftiness and height of each of the surfaces (16, 18) of the scrubbing article 10.
  • the surfaces 16, 18 may be visually distinct from one another, meaning that they are readily discernable to the naked eye such as depicted in FIG. 6A, described below.
  • the first degree of loftiness i.e., the degree of loftiness associated with the first surface 16
  • the second degree of loftiness i.e., the degree of loftiness associated with the second surface 18
  • the first height hi i.e., the height associated with the first surface 16
  • the second height h 2 i.e., the height associated with the second surface 18.
  • the degree of loftiness is better illustrated by the "openness" of the fibers 50a.
  • the fibers 50a are more distinctly spaced apart as compared to the fibers 50b.
  • the first surface 16 can be described as having fewer fibers 50 per unit volume as compared to the number of fibers 50 per unit volume of the second surface 18.
  • this difference in degree of loftiness or fibers per unit volume can be achieved by treating the substrate 12 at the second surface 18 or may be accomplished during the fabric forming process by forming (e.g., knitting, weaving) the substrate 12 to have a more dense (less lofty, flatter) structure at the second surface 18.
  • the bulk density of the first surface 16 is at least 100% less than the bulk density of the second surface 18, more preferably at least 200% less than, and even more preferably at least 300% less than. It will be understood that by having a lesser bulk density, the first degree of loftiness (of the first surface 16) is thus greater than the second degree of loftiness (of the second surface 18) as bulk density has an inverse relationship with loftiness.
  • the fibers 50 (encompassing fibers 50a and 50b) comprising the substrate 12 are, in one embodiment, randomly or semi-randomly dispersed within the substrate 12.
  • the scrubbing cloth 10 at the surface 16 may not have clear “edges”.
  • various ones of the fibers 50a “extend” or project beyond hypothetical edges of the cloth 10 (shown with dashed lines in FIG. 5 A).
  • the fibers 50b may provide a more clear edge.
  • the "height" of a particular surface can be more accurately described as the nominal height defined by a majority of the fibers 50a, 50b positioned/extending at the surface 16, 18.
  • the fibers 50a combine to define a height of the first surface 16 and the fibers 50b combine to define a height of the second surface 18.
  • the height of the first surface 16 is at least 120% of the height of the second surface 18, more preferably at least 150%, and even more preferably at least 200%.
  • the first surface 16 extends higher or farther beyond the mid-plane M than does the second surface 18.
  • the degree of loftiness and height of opposed sides 16, 18 of substrate 10 may be substantially equal.
  • one side e.g., 16
  • one side may be treated to form a side having a greater (or lesser) degree of absorptiveness than an opposed side (e.g., 18).
  • FIG. 13 illustrates an embodiment of a scrubbing cloth 10 having opposed sides or surfaces 16, 18 and a texture layer 14 formed on surface 18.
  • the relative degrees of loftiness and height of surfaces 16, 18 are substantially the same or equal.
  • side 16 is treated such as by a chemical, physical or other method to provide fibers 50a, and thus side 16, with a relatively greater absorptive quality (i.e., more absorptive) than that of fibers 50b and therefore that of side 18.
  • Some chemical and physical treatments include plasma treatment, flame treatment, electrical discharge and/or spraying or otherwise depositing a chemical composition onto one side of the substrate 12 used to form cloth 10. What is important is that the treatment creates fibers (e.g., 50a) having a relatively more (or less) absorptive quality than the fibers (e.g., 50b) of an opposed side of the substrate 12. Further, even where a substrate 12 is formed as described above to have one relatively more lofty, less dense, higher fiber side (e.g., 16), one side of the substrate may be treated as described above, chemically or physically to provide additional levels of relative absorption of the surfaces 16, 18 of a substrate 12.
  • the substrate 12 may be formed from a variety of materials and in a variety of forms.
  • Any substrate material or combination of materials suitable for use as a consumer scrubbing cloth can be used including, without limitation, various woven, knitted, and non-woven materials.
  • the materials and forms of the substrate 12 can be selected to provide varying ranges of desired properties, such as extensibility, elasticity, durability, flexibility, etc., that are particularly suited to a given scrubbing task and/or are particularly suited to depositing or forming of a texture composition thereon.
  • the durability of materials suitable for use in scrubbing cloths is often categorized as "disposable” (meaning that an cloth formed from the material is intended to be discarded immediately after use), “semi-disposable” (meaning that an article formed from the material can be washed and re-used a limited number of times), or “reusable” (meaning that an article formed from the material is intended to be washed and re-used).
  • Materials useful for substrate 12 may be selected to have durability properties in a wide range (i.e., disposable, semi-disposable or reusable), but may be particularly chosen to have reusable properties.
  • materials may be selected based upon their flexibility.
  • a relatively more flexible, supple scrubbing article is preferred (e.g., drapable)
  • providing a more flexible substrate 12 allows the user to readily fold, squeeze, or otherwise manipulate the scrubbing article 10 in a manner most appropriate for the particular scrubbing task.
  • the desired suppleness of the substrate 12 is best described with reference to a dry basis weight thereof.
  • a nonwoven substrate 12 of the present disclosure has a dry basis weight of less than about 300 g/m 2 , but preferably greater than about 30 g/m 2 . In other embodiments, the nonwoven substrate 12 has a dry basis weight of less than about 200 g/m 2 .
  • the suppleness of the nonwoven substrate 12 can be expressed in terms of drapability.
  • “Drapability” is defined as the inherent ability to conform to an irregular or non-flat surface. Drapability or “drape” is measured using INDA standard for "Handle-O-Meter Stiffness of Nonwoven Fabrics” 1ST 90.3 (95). With this in mind, the nonwoven substrate 12 preferably has a drapability value of less than about 250.
  • Exemplary substrates 12 used to form the fabric of the present disclosure will now be described, however, a wide variety of materials may be used for substrate 12, as noted above.
  • Exemplary fabrics useful with the present disclosure include a knitted fabric prepared from 82% poly(ethylene terephthalate) and 18% polyamide 6 fibers having a thickness in a range of 0.45-0.75 mm and a unit weight of 160 grams per square meter.
  • Nonwovens likewise may be used and can be formed from a variety of materials and in a variety of fashions selected to provide desired properties, such as extensibility, elasticity, etc., in addition to the requisite suppleness.
  • a nonwoven is comprised of individual fibers (e.g., 50, FIG. 1) entangled with one another (and optionally bonded) in a desired fashion.
  • the fibers are preferably synthetic or manufactured, but may include natural materials such as wood pulp fiber.
  • the term "fiber” includes fibers of indefinite length (e.g., filaments) and fibers of discrete length (e.g., staple fibers).
  • the fibers used in connection with a nonwoven substrate 12 may be multicomponent fibers.
  • multicomponent fiber refers to a fiber having at least two distinct longitudinally coextensive structured polymer domains in the fiber cross- section, as opposed to blends where the domains tend to be dispersed, random, or unstructured.
  • the distinct domains may thus be formed of polymers from different polymer classes (e.g., nylon and polypropylene) or be formed of polymers of the same polymer class (e.g., nylon) but which differ in their properties or characteristics.
  • multicomponent fiber is thus intended to include, but is not limited to, concentric and eccentric sheath-fiber structures, symmetric and asymmetric side-by-side fiber structures, island-in-sea fiber structures, pie wedge fiber structures, and hollow fibers of these configurations.
  • suitable processes for making the nonwoven substrate 12 include, but are not limited to, spunbond, blown microfiber (BMF), thermal bonded, wet laid, air laid, resin bonded, spunlaced, ultrasonically bonded, etc.
  • the substrate 12 is spunlaced utilizing a fiber sized in accordance with known spunlace processing techniques.
  • one construction of a nonwoven substrate 12 is a blend of 50/50 wt. % 1.5 denier polyester and 1.5 denier rayon at 50 - 60 g/m 2 .
  • the substrate 12 is first carded and then entangled via high-pressure water jets as is known in the art.
  • the spunlace technique eliminates the need for a thermal resin bonding component, so that the resulting nonwoven substrate is amenable to being loaded with virtually any type of chemical solution (i.e., anionic, cationic, or neutral).
  • An exemplary nonwoven includes a thermally point-bonded spunbond poly(ethylene terephthalate) nonwoven.
  • the substrate 12 is highly flexible and drapable and conducive to use and handling by a user otherwise using the article 10 for scrubbing purposes and is selected having regard to the intended use of the scrubbing cloth 10. Further embodiments, can include one or more additional layers on the surface 16, 18 of the substrate 12 such as an adhesion promoter layer or a tie layer, for example.
  • substrate 12 may be formed to have differing degrees of loft, height and relative "flatness'V'fluff' on opposed sides 16, 18.
  • forming the substrate 12 to include these features may be accomplished in a variety of ways.
  • the substrate 12 can be formed in the first instance, or upon manufacturing of the fabric 12, such that the opposed sides 16, 18 include the varying (different) features immediately after manufacture of the fabric 12, without undergoing any further processing.
  • a substrate 12 may be first formed into a fabric and subsequently one side (e.g., 18, FIG.
  • the fabric can be treated to provide a less lofty, flatter or lower in height surface while the opposed side (e.g., 16) is not subjected to the same treatment thereby resulting in a loftier, more open, higher opposing, untreated surface.
  • FIGS. 6A-6B are photographs of an example substrate 12 and scrubbing cloth 10 formed according to these methods.
  • substrate 12 forms a fabric 12 that, in the illustrated view, is folded upon itself (e.g., in half) at a fold F and has corner C of the folded fabric folded back upon itself to expose a surface 18.
  • the fabric 12 of FIG. 6 A was initially formed according to the EXAMPLES, SAMPLE 1, set forth below.
  • One side 18 of the fabric forms a lower plane of the fabric having a relatively flat surface while the opposed side 16 of the fabric 12 includes fibers (e.g., 50) projecting in a direction outwardly opposed to d surface 18 to form a relatively fluffy, loftier surface 16.
  • Fabrics/substrates 12 formed according to these embodiments may advantageously allow for ease of deposition or formation of a texture layer 14 on the flat surface 18 in that providing a surface that is relatively flat or smooth can allow for a well-defined, sharp texture pattern to be deposited thereon.
  • a texture layer may alternatively be formed on the lofty, fluffy surface (e.g., 16) of a substrate 12 formed in the manner described above.
  • FIG. 6B is a photograph of the flat, less lofty surface 18 of substrate 12 of FIG. 6A after a texture layer 14 has been formed thereon, thereby forming the surface 18 of a scrubbing cloth 10.
  • one side of substrate 12 may be treated to temporarily or permanently create a less lofty, flatmore dense surface, or at least portions thereof 16.
  • Treatment of a surface can include various processing methods including but not limited to: calendaring, heat compression, flame treating, ultrasound treating, melting, cutting, and removing fiber height. These processing methods in turn can take on various forms and may be accomplished in a variety of ways. Some of these methods can create only a permanent or only a temporarily flatter/denser/consolidated surface (or at least portions of the surface) whereas some of these methods can create either a permanent or a temporarily flatter/denser/consolidated surface or portions of the surface), depending upon processing parameters.
  • FIG. 10 illustrates a substrate 12 with opposed sides or surfaces 16, 18a where surface 18a depicts surface 18 in an untreated, first or original state.
  • Surfaces 16 and 18a are of uniform loft, height and relative "fluffiness.”
  • One side (surface 18, referenced generally) of the fabric 12 is subjected to treatment in any manner discussed above via a fabric treatment device 60.
  • Device 60 can include for example a heated nip roller, cutter, press, heated press etc. Regardless, subjecting surface 18 to treatment creates a second or treated state 18b (referenced generally) that forms the flattened, consolidated or otherwise treated second surface 18b.
  • a texture layer (not pictured in FIG. 10) may be formed on either surface 16, 18b as described below, to form a scrubbing cloth 10 (FIG. 1).
  • one side 18 of substrate 12 is only temporarily flattened
  • FIGS. 11 and 12 illustrate a texture layer 14 is formed on the temporarily flattened surface.
  • the temporarily flattened surface, having texture layer 14 includes surface portions that do not have a texture composition deposited thereon and these portions are allowed to return to an unflattened state.
  • substrate 12 includes a temporarily consolidated surface 18b.
  • Surface 18b has been previously flattened such as via a treatment device 60 (FIG. 10).
  • a texture layer 14 is deposited on surface 18b via a texture former 58.
  • FIG. 12 illustrates the textured scrubbing cloth 10 of FIG.
  • FIGS. 7A-7B are photographs of an example scrubbing cloth 10 formed according to the present disclosure and as provided in the EXAMPLES, SAMPLE 2, set forth below. As described below, FIG. 7A is a photograph of one side of a substrate 12 formed from a non woven microfiber cloth 12.
  • discrete portions may extend or proj ect outwardly from the surface 16, 18 at substantially uniform distances or, alternatively, may extend or project outwardly from the surface 16, 18 at varying distances (i.e. the discrete portions 20a, 20b can have similar or varying heights with respect to the surface 16, 18).
  • discrete portions e.g., 20a, 20b
  • discrete portions e.g., 20a, 20b
  • discrete portions may extend to any distance in a range of about 10 to about 20 microns outwardly from the surface 16, 18.
  • FIG. 8 illustrates a scrubbing cloth 10 in a position such that the surface (e.g., 18) having the texture layer 14 formed thereon is facing the surface 30 to be scrubbed.
  • the scrubbing cloth 10 is positioned to clean or otherwise treat surface 30.
  • the surface 30 to be cleaned is application specific, and can be relatively hard (e.g., a table top or cooking pan) or relatively soft (e.g., human skin, polymeric baking vessels, etc.).
  • the surface 30 to be scrubbed may have a mass 32 that is undesirably affixed thereto.
  • the mass 32 will be unique to the particular scrubbing application, but includes matters such as dirt, dried food, dried blood, etc.
  • the scrubbing cloth 10 and in particular the surface having a textured layer 14 thereon facilitates scrubbing removal of the mass 32 as a user repeatedly forces the texture layer 14 (or a portion or section thereof) back and forth across the mass 32.
  • Each section (for example, the portions 20a, 20b) of the texture layer 14 must be sufficiently hard to either abrade or entirely remove the mass 32 during the scrubbing motion.
  • the discrete portions (for example, the portions 20a, 20b) provided by the texture layer 14 of the present disclosure be sufficiently spaced from one another to ensure intimate contact between the mass 32 and the sidewall 42 of the particular texture layer portion 20a, 20b during a cleaning operation.
  • the texture layer 14 has abrasion resistance such that the composition forming the texture layer 14 remains substantially intact on the substrate 12 during and after the cloth 10 is used to scrub a surface 30.
  • the texture layer 14 of the present disclosure may be configured to have a relative hardness at least equal to or greater than the hardness of the substrate 12 to which the layer is imparted, as briefly referred to above.
  • the local hardness of the texture layer portions e.g., 20a, 20b
  • overall texture layer 14 is equal to or greater than the hardness of the entire cloth 10, or the "global hardness”.
  • Cloth 10 may thus be defined as having global flexibility, since the substrate 12 is softer or more flexible in relation to the harder, less flexible abrasive/texture layer 14.
  • Hardness of a texture composition 14 after having been formed on a substrate as well as hardness of a substrate (for comparison) can be achieved in a number of ways.
  • hardness of a material can be established by determining the Rockwell indentation hardness, such as described in ASTM El 8 - 14a: Standard Test Methods for Rockwell Hardness of Metallic Materials; by determining Knoop and Vickers hardness, such as described in ASTM E384 - 10: Standard Test Method for Knoop and Vickers Hardness of Materials; by determining the durometer hardness, such as described in ASTM D2240 - 05: Standard Test Method for Rubber Property— Durometer Hardness, or by determining the Brinell hardness, such as described in ASTM E10 - 14: Standard Test Method for Brinell Hardness of Metallic Materials.
  • a cloth having the above characteristics is uniquely useful as a scrubbing article in that the cloth is sufficiently flexible to allow a user to make contact in, on and about a variety of objects to be scrubbed, while the hardness of the abrasive layer provides the desired scrubbing performance.
  • the texture layer 14 is formed on a fluffier, loftier or more absorbent surface (e.g., 16), while portions of the surface 16 may impart a mild wiping action to the surface 30, it remains that the texture layer 14 will nevertheless provide a more abrasive side 16 and a non-abrasive side 18.
  • the flat, less lofty surface 18 may be utilized to perform a wiping, absorbing or non-abrasive function.
  • a multipurpose scrubbing cloth is formed from a single substrate layer (i.e., non-laminated, uniform) and can perform multiple functions depending upon the surface 16, 18 that is applied to a targeted object to be treated.
  • compositions of the texture layer 14 will include a selected resin and may include additional constituents such as mineral(s), filler(s), colorant(s), thickener(s), defoaming agent(s), surfactant(s), soaps, or other cleaning/disinfecting/sanitizing agents etc.
  • the texture layer 14 may optionally be e-beam treatable/treated and may include compositions such as described U.S. Provisional Patent Application Serial No. 62/121,766, entitled “Scrubbing Article and Method of Making Same” filed on February 27, 2015 and incorporated by reference herein in its entirety.
  • the texture layer 14 may be UV treatable/treated or crosslinked and may include compositions such as described in U.S. Provisional Patent Application Serial No. 62/121,705, entitled, "UV Treated Scrubbing Articles and Methods of Making Same” filed on February 27, 2015 and incorporated by reference herein in its entirety.
  • texture layer 14 comprises a resin composition and may comprise various polymers and/or monomers.
  • Some acceptable resins include those resins selected from the group consisting of polyolefins, styrene-butadiene resin, acrylic resin, phenolic resin, nitrile resin, ethylene vinyl acetate resin, polyurethane resin, styrene-acrylic resin, vinyl acrylic resin and combinations thereof.
  • the resins may be provided as monomers, oligomers, polymers, or combination thereof.
  • Monomers may include multifunctional monomers capable of forming a crosslinked structure, such as epoxy monomers, olefins, styrene, butadiene, acrylic monomers, phenolic monomers, substituted phenolic monomers, nitrile monomers, ethylene vinyl acetate monomer, isocyanates, acrylic monomers, vinyl acrylic monomer and combinations thereof.
  • materials may be selected to have molecular weights or viscosities allowing the texture layer 14 composition to be flowable in a manner that will fill the holes or voids of stencil pattern during transfer or printing of the composition to a substrate 12, sufficiently adhere to, and perhaps penetrate, the substrate 12 and to hold the desired pattern shape upon removal of the stencil from the substrate 12, even prior to (though especially subsequent to) additional processing such as rest or wait periods, heat treatment (evaporation) or optional e-beam or UV treatment.
  • the viscosity of a texture layer 14 composition may be selected to provide a sharp pattern. Lower viscosity mixtures may have a tendency to result in printed (or coated) droplets of mixture that almost immediately coalesce on a substrate and form a continuous film rather than discreet droplets, as often desirable for obtaining a sharp pattern.
  • an initiator, a promoter, or a retardant can optionally be provided as part of the formulation or composition of texture layer 14, according to some embodiments of the present disclosure, as described in detail in Provisional Patent Application Serial No. 62/121,766, incorporated by reference herein above.
  • the particulate component additive comprises less than 70% by weight of the texture layer 14, more preferably less than 50% by weight, most preferably less than 30% by weight.
  • the particulate component may consist of inorganic, hard, and small particles.
  • the "Minex" mineral particulate component has a median particle size of 2 microns and a Knoop hardness of about 560. Of course, other particle size and hardness values may also be useful.
  • the inorganic nature of the particulate component, in conjunction with the non-ionic resin component renders the resulting texture layer 14 amenable for use with any type of chemical solution.
  • the texture layer 14 can further include a colorant or pigment additive to provide a desired aesthetic appeal to the wiping article 10.
  • a colorant or pigment additive to provide a desired aesthetic appeal to the wiping article 10.
  • Appropriate pigments are well known in the art, and include, for example, products sold under the trade name SUNSPERSE, available from Sun Chemical Corp. of Amelia, Ohio.
  • Other coloring agents as known in the art are equally acceptable and in some embodiments comprise less than 10% of the texture layer composition by weight.
  • the texture layer composition can include a thickening agent or agents to achieve a viscosity most desirable for the particular printing technique employed and speed of the manufacturing line.
  • appropriate thickening agents are known in the art and include, for example, methylcellulose and a material available under the trade name "RHEOLATE 255" from Rheox, Inc. of Hightstown, New Jersey.
  • Another acceptable thickening agent is available from Huntsman International LLC, High Point, NC, USA under the trade designation of LYOPRINT PT-XN.
  • a thickening agent may be unnecessary depending upon the selected resin and printing technique; however, where employed, the thickening agent preferably comprises less than approximately 40% by weight of the texture layer composition.
  • a salt component may be provided in the composition to aid in causing an ionic reaction between components of an emulsion and thereby likewise generate an increase in the viscosity of the composition, as is known in the art.
  • the composition of texture layer 14 may be non-ionic, according to some embodiments.
  • anti-foaming agents may be included in the composition to provide defoaming or emulsification of the composition.
  • carrier oils such as water-insoluble paraffinic and naphthenic mineral oils, vegetable oils, tall oil, castor oil, soybean oil, peanut oil; silicone oils, such as dimethylpolysiloxanes; hydrophobic silica; Hydrophobic fat derivatives and waxes, such as fatty acid esters of monofunctional and polyfunctional alcohols, fatty acid amides and sulfonamides, paraffinic hydrocarbon waxes, ozokerite, and montan wax, phosphoric acid mono-, di-, and triesters of short- and long-chain fatty alcohols, short- and long-chain natural or synthetic fatty alcohols, water-insoluble soaps of long-chain fatty acids, including aluminum stearate, calcium stearate, and calcium be
  • the composition of the texture layer 14 may include binder resins, ceramic microparticles or processing agents as described in U.S. Provisional Patent Application Serial No. 62/121,644 , entitled, "Consumer Scrubbing Article with Ceramic Microparticles and Method of Making Same” filed on February 27, 2015 and incorporated by referenced herein in its entirety.
  • the SAMPLE 2 substrate was treated via consolidating one side via heated steel rolls with a nip.
  • the steel rolls were heated, starting at room temperature and increased to greater than 204°C. It was observed that the roll speed has an impact on the heat dwell time, which can impact the amount of the consolidation present on the cloth.
  • One of the rolls was heated to a higher temperature than the other, providing consolidation on one side while the opposed side remained undisturbed. It was likewise observed that the lower temperature roll would not necessarily need to be heated.
  • a gap was also set between the rolls in order to not compress SAMPLE 2 completely flat.
  • the initial thickness of the substrate was 3.2 mm prior to consolidating one surface. After consolidating, an approximate thickness of the same cloth was found to be 2.0mm.
  • a metal stencil was placed on top of the substrate specimen.
  • the metal stencil included the texture pattern shown in FIG. 1
  • the metal stencil included the texture pattern shown in FIG. 9B.
  • Approximately 100 grams of the prepared printing composition was placed on the stencil with the help of a wooden applicator.
  • the printing mixture was then applied on the printing pattern of the stencil with a shearing motion while applying hand pressure downwards and with the help of a hand-held squeegee. It was observed that for each specimen, the printing mixture filled the holes of the printing pattern and was transferred onto the substrate specimen. Then, the stencil was removed and the printed substrate specimen was left undisturbed on a laboratory bench for 10 minutes.
  • Scrubbing cloths according to the present disclosure may uniquely satisfy various cleaning or scrubbing requirements in a singular cleaning article. In this manner, scrubbing cloths according to the disclosure may be considered multipurpose scrubbing cloths.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un tissu de nettoyage ayant des première et seconde surfaces opposées formées de sorte à avoir des propriétés différentes l'une par rapport à l'autre et une couche de texture formée sur la première surface et/ou la seconde surface afin de fournir un tissu de nettoyage à usages multiples présentant des capacités de traitement de surface améliorées.
EP16706786.7A 2015-02-27 2016-02-04 Tissus de nettoyage grand public à usages multiples et leurs procédés de fabrication Active EP3082547B1 (fr)

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US201562121808P 2015-02-27 2015-02-27
PCT/US2016/016535 WO2016137708A1 (fr) 2015-02-27 2016-02-04 Tissus de nettoyage grand public à usages multiples et leurs procédés de fabrication

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CN (1) CN106103077B (fr)
ES (1) ES2674895T3 (fr)
MX (1) MX2016003383A (fr)
TR (1) TR201808824T4 (fr)
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KR20170113530A (ko) 2017-10-12
TW201635962A (zh) 2016-10-16
KR20160114033A (ko) 2016-10-04
WO2016137708A1 (fr) 2016-09-01
MX2016003383A (es) 2016-11-28
EP3082547B1 (fr) 2018-03-28
CN106103077A (zh) 2016-11-09
CN106103077B (zh) 2018-06-12
ES2674895T3 (es) 2018-07-04
US20160367103A1 (en) 2016-12-22
JP2018506415A (ja) 2018-03-08
TR201808824T4 (tr) 2018-07-23

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